Synthesis of unsaturated amino alcohols through unexpectedly selective Ru-catalyzed cross-metathesis reactions

Organic Letters

Volumn 7, Issue 11, 2005, Pages 2113-2116

  Hoveyda, Hamid R ^a   Vézina, Martin ^a  

^a UNIVERSITÉ DE SHERBROOKE   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; AMINOALCOHOL; CYANIDE; NITRILE; RUTHENIUM; RUTHENIUM COMPLEX;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CONCENTRATION (PARAMETERS); REDUCTION; SYNTHESIS;

EID: 20444463492     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol050387g     Document Type: Article

References (42)

1. For recent general reviews on CM, see: (a) Chatterjee, A. K. In Handbook of Metathesis; Grubbs, R. H, Ed.; Wiley-VCH: Weinheim, Germany, 2003; Vol. 2, Chapter 2.8, pp 246-295.
2. (b) Connon, S. J.; Blechert, S. Angew. Chem., Int. Ed. 2003, 42, 1900-1923.
3. (a) Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360-11370 and references therein.
4. (b) Blackwell, H. E.; O'Leary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58-71. Lack of control over E/Z stereoselectivity is an additional problem in catalytic CM reactions. As noted in ref 2a, a further complication is that product selectivity and stereoselectivity are influenced by one another as a result of secondary metathesis reactions.
5. (a) Crowe, W. E.; Zhang, Z. J. J. Am. Chem. Soc. 1993, 115, 10998-10999.
6. (b) Crowe, W. E.; Goldberg, D. R. J. Am. Chem. Soc. 1995, 117, 5162-5163.
7. 3), 4, was employed in these early studies.
8. Only Ru complexes 1 and 2 and Mo complex 4 were included in their report (cf. ref 2a).
9. Ru-catalyzed CM with N-protected allylamine (Type I) is not a viable option due to conversion to enamines. See: (a) Toste, F. D.; Chatterjee, A. K.; Grubbs, R. H. Pure Appl. Chem. 2002, 74, 7-10.
10. 1H NMR) in ≤5% after partial purification.
11. Acrylonitrile is absent from Grubbs' olefin categorization with 1 and 2 (cf. ref 2a). Given the reluctance of acrylonitrile to undergo homodimerization, it is perhaps best to categorize this alkene as a Type III with 3 and as a Type IV with complexes 1 or 2.
12. (a) For a review of Hoveyda-Grubbs Ru catalysts, see: Hoveyda, A. H.; Gillingham, D. G.; Van Veldhuizen, J. J.; Kataoka, O.; Garber, S. B.; Kingsbury, J. S.; Harrity, J. P. A. Org. Biol. Chem. 2004, 2, 8-23 and references therein.
13. (b) A study of CM reaction using 3 and involving unsaturated alcohols was reported by: Cossy, J.; BouzBouz, S.; Hoveyda, A. H. J. Organomet. Chem. 2001, 624, 327-332.
14. (c) For a phosphine-free variant of 2 that effects CM of acrylonitrile; see: Love, J. A.; Morgan, J. P.; Trnka, T. M.; Grubbs, R. H. Angew. Chem., Int. Ed. 2002, 41, 4035-4037.
15. (a) Randl, S.; Gessler, S.; Wakamatsu, H.; Blechert, S. Synlett 2001 430-432.
16. (b) Gessler, S.; Randl, S.; Blechert, S. Tetrahedron Lett. 2000, 41, 9973-9976.
17. For reports describing the attempted use of allyl cyanide in CM reactions, see: (a) Giger, T.; Wigger, M.; Audétat, S.; Benner, S. A. Synlett 1998, 688-691.
18. (b) BouzBouz, S.; Simmons, R.; Cossy, J. Org. Lett. 2004, 6, 3465-3467. No CM product was obtained with 1 (ref 9a). (Thus, allyl cyanide might be considered as a Type IV olefin with 1; cf. Table 1, entry 4.) In the example described in ref 9b, a substatistical yield of 23% was obtained with 3, and this low yield was attributed to the "presence of a cyano group".
19. (a) Homodimers of 5c (7% isolated yield) and 6b (5%) (Table 1, entry 6) were generated as side-products. Moreover, when this reaction was conducted using 1.1 equiv of allyl cyanide, 7b was obtained in 72% yield and homodimers 5c and 6b were isolated in 7 and 11% isolated yields, respectively.
20. (b) For a study on the impact of concentration in RCM, see: Yamamoto, K.; Biswas, K.; Gaul, C.; Danishefsky, S. J. Tetrahedron Lett. 2003, 44, 3297-3299.
21. Conditions shown for synthesis of 7c were not fully optimized.
22. As discussed in ref 2a, the higher quantities of the thermodynamically favored E isomer may be a reflection of the comparative ability of 7a and 7b to undergo E/Z isomerization through secondary metathesis processes.
23. Conditions refined for 7b (Table 1, entry 6) may not be optimal for these other substrates (in Table 2). Nevertheless, inasmuch as the general trends reveal, the results in Table 2 aid in demarcating the scope of CM reactions with allyl cyanide.
24. 13C).
25. Conducting CM reaction with 10 for 16 h, a duration comparable to that used in ref 2a, resulted in a similar yield of 24%. The homodimer of 10 was the major side-product isolated (24% yield); the homodimer of allyl cyanide (6b) was also obtained in <2% yield.
26. As expected, matching Type I/II cross partners resulted in slightly improved CM selectivity (cf. Table 2, entries 1 vs 6).
27. For studies on chelation effects in CM, see: (a) BouzBouz, S.; Cossy, J. Org. Lett. 2001, 3, 1451-1454.
28. (b) Engelhardt, F. C.; Schmitt, M. J.; Taylor, R. E. Org. Lett. 2001, 3, 2209-2212.
29. (c) Smulik, J. A.; Diver, S. T. Org. Lett. 2000, 2, 2271-2274.
30. (d) For the effect of free allylic hydroxyl group on the RCM reaction rates, see: Hoye, T. R.; Zhao, H. Org. Lett. 1999, 7, 1123-1125.
31. 1H COSY, GC-MS). This adventitious product is likely the result of olefin isomerization (in 5c) followed by CM. For other related examples, see: Alcaide, B.; Almendros, P. Chem. Eur. J. 2003, 9, 1259-1262 and references therein.
32. Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6453-6554.
33. Ahn Y. M.; Yang, K.; Georg, G. I. Org. Lett. 2001, 3, 1411-1413.
34. This crude residue was immediately passed through a short silica gel column (EtOAc/hexanes 3:1) to remove the bulk of the colored impurity. The final purification can be postponed, if necessary.
35. Cimino, G.; Gavagnin, M.; Sodano, G.; Spinella, A.; Strazzullo, G.; Schmitz, F.; Yalamanchili, G. J. Org. Chem. 1987, 52, 2301-2303.
36. (a) Using conditions reported in: Dolle, R. E.; Nicolaou J. Am. Chem. Soc. 1985, 107, 1691-1694.
37. Gallagher, T. F.; Adams, J. L. J. Org. Chem. 1992, 57, 3347-3353.
38. (b) This side-reaction ensues when the attack of the primary amine onto the intermediate imine proceeds more rapidly than the corresponding hydride attack. See: Gould, F. E.; Johnson, G. S.; Ferris, A. F. J. Org. Chem. 1960, 25, 1658-1660.
39. Osby, J. O.; Ganem, B. Tetrahedron Lett. 1995, 26, 6413-6416.
40. Caddick, S.; Haynes, A. K. de K.; Judd, D. B.; Williams, M. R. V. Tetrahedron Lett. 2000, 41, 3513-3516.
41. 4 (cf.: Ganem, B.; Osby, J. O. Chem Rev. 1986, 86, 763-780 and references therein)
42. and (ii) a variant of strategy i, whereby the protection of the primary amine group is effected in a one-pot manner; however, this procedure, in contrast to that in Scheme 2, fully reduces conjugated nitrile moieties (cf. entries 14 and 15 in: Caddick, S.; Judd, D. B.; Lewis, A. K. de K.; Reich, M. T.; Williams, M. R. V. Tetrahedron 2003, 59, 5417-5423).